Textile-decorating compositions



Patented Oct. 5, 1954 ATE? ()FFICE Arthur Booth, Little Falls, N. 3.,assignor to Intercnemical Corporation, New York, N. Y., a corporation of()hio No Drawing. Application October 8, 1947, Serial No. 778,727

(Cl. 2i39--22) 8 Claims.

This invention relates to the pigment-decoration of textiles and isparticularly concerned with the use in the dyeing and the printing offabrics and textile materials of a composition comprising an aqueousphase containing a dispersed water-insoluble film-forming resinemulsified in a pigmented. lacquer phase in which the dispersedwater-insoluble resin is also insoluble. The present application is acontinuation-in-part of my copending applications, Serial No. 666,189,filed April 30, 1946, and Serial No. 7%,803, filed April 29, 1947, bothof which applications are now abandoned.

Compositions comprising an aqueous medium, usually water, emulsified asthe inner phase in an outer pigmented lacquer phase containing a pigmentbinder, generally an organic solventsoluble thermosetting resin, havegone into extensive use in the printing and the dyeing of textiles andsimilar fabrics. The application of such a pigmented emulsion in theprinting of textile fabrics is disclosed in Jenett, 2,222,581, and2,222,582; and the application thereof in the dyeing of fabrics isdisclosed in Cassel, 2,248,696.

The use of these pigmented Water-in-lacquer emulsions in the printing orthe dyeing of textiles has obvious advantages in that pigments, whichare generally cheaper and more light-resistant than dyestufis, can beemployed, the emulsion provides a low-cost vehicle for the pigment, andthe pigmented emulsion can be easily applied to a fabric. In addition,an unusual sharpness of detail is obtained in the resulting printedtextile. Moreover, a soft hand is imparted to the printed or dyed fabricbecause the binder cements the pigment to the structural fibers of theindividual yarns of the fabric in the form of completely discontinuousfilms and does not bridge over the yarns with a continuous film.

The resulting pigment-printed or -dyed textile has the disadvantage,however, that it tends to crock to some extent, i. e., to yield aportion of its color to another material such as another fabric, forexample, when the latter is rubbed thereover. Fabrics printed or dyed indeep shades exhibit the greatest tendency to crock, and the fullutilization of pigments in the decoration of fabrics is thereby limited.

Various procedures have been suggested heretofore for elimination orreduction of this tend" ency of such pigment-colored fabrics to crockbut all are objectionable for one reason or another. For example, thedegree of crocking can be readily reduced by overpadding thepigmentprinted or -dyed textile material with a solution of a suitableresin in an organic solvent and then heating the fabric to set and curethe resin. This process, however, is expensive and also re quires adouble treatment of the fabric, an operation that the trade resists. Thedegree of orocking can also be reduced by incorporating a larger amountof resin in the lacquer phase. This procedure is likewise expensive and,in addition, there is frequently also a loss of color value.Furthermore, both procedures generally result in the production of afinished fabric having an objectionable boardiness or stifi'ness.

I have now discovered that the crockfastness of such a pigment-printedor -dyed fabric can be unexpectedly and materially improved, with.- outimparting an objectionable hand or boardiness to the finished fabric andwith improvement in the color value, by utilizing as the printing pasteor the dye bath an aqueous dispersion of a water-insoluble film-formingresin emulsified in an outer pigmented lacquer phase in which thedispersed Water-insoluble resin is also insoluble. Advantageously, incarrying out the present invention, I utilize a textile-decoratingcomposition comprising a dispersion of a water-insoluble film-formingelastomerio' resin in an aqueous phase emulsified in an outer pigmentedlacquer phase comprising a solution of a thermosetting resin in avolatile organic solvent in which the water-dispersed elastomer is alsoinsoluble.

My textile-decorating composition in its simplest form comprisesessentially a dispersion of a film-forming water-insoluble resin in anaqueous phase that is emulsified in an outer pigmented phase in whichthe dispersed Water-insoluble resin is also insoluble. I have obtainedespecially good results with a composition in which the water-insolubleresin comprises a filmtorming elastomer. In its preferred form, mycomposition comprises a dispersion of a filmiorming Water-insolublesynthetic elastomer in an aoueous phase emulsified in an outer pigmentedper phase consisting essentially of a solution of a pigment-binder,advantageously a thermo resin, in a volatile organic solvent in whichthe elastomer is also insoluble.

Any pigment can be incorporated into the lacquer phase of the presentcomposition, but the pigment employed in any particular applicationshould be selected in view of the nature of the finished goods and theexpected use thereof; that is, it should be satisfactorily lightfast, ifnecessary it should not bleed to any substantial-extent in dry-cleaningsolvents such as naphtha and carbon tetrachloride, it should beresistant to soap to the degree required, or the like. Typical pigmentsinclude the phthalocyanines, various metal oxides, carbon black,water-insoluble vat and azo dyestuffs, and the like.

While the lacquer phase may comprise a simple dispersionwof the pigmentin a-suitable volatile organic solvent in those cases where the washfastness of the decorated fabric is of no moment, an organicsolvent-soluble binder is preferably also incorporated in this phase inorder to impart washand scrub-resistance to the finished textilematerial. This binder may comprise any suitable plastic or solidfilm-forming, water-resistant material such as a cellulose derivative,e. g., ethyl cellulose, or a resin that is soluble in the organicsolvents comprising the lacquer phase and insoluble in water (theaqueous phase). Advantageously, however, a film-forming thermosettingresin is utilized as the binder. Various types of water-insoluble,organic solvent-soluble .thermosetting resins including urea-aldehyderesins .such as urea-formaldehyderesins, -melaminealdehyde resinsincluding melamine-formaldehyde resins, phenol-aldehyde resins includingphenol-formaldehyde resins, drying oil-modified alkyd resins, and thelike, can be used for this purpose. To be suitable for this purpose,moreover, the thermosetting resin,.or other binder, after application ofthe emulsion to the fabric and heating of the 'fabric .to dry it and, asthe case may be, to convert the resin or other binder to asolvent-insoluble state, must be sufiiciently resistant to washing andmust be substantially insoluble in customary dry-cleaning solvents andmust impart no objectionable stiffness to the finished fabric.

The resin dispersed in thezaqueous phase of my improvedtextile-decorating composition may comprise any film-formingwater-insoluble resinous material that is also insoluble in the organicsolvent'or solvents comprising the outer lacquer phase. Typicalresins-meeting these requirements include various resins formed fromacrylic acid and its derivatives such as .acrylate resins andmethacrylate resins, various vinyl halide resins,

especially vinyl chloride polymers and copolymers forming syntheticelastomer is dispersed in the aqueous phase, and I prefer to employ sucha synthetic elastomer as the water-dispersed resin in the presentcomposition. Advantageously, the water-dispersed resin comprises asuitable copolymer of butadiene and acrylonitrile. Two or morefilm-forming water-insoluble resins may, of course, be dispersed in theaqueous phase if desired; and a particularly good degree ofcrockresistance can be obtained with a mixture of abutadiene-acrylonitrile copolymer and an acrylic acid-ester polymer.

(The term elastomer as used herein is employed in accordance with thedefinition thereof generally accepted in the art and given on pages 942and 944 in the articleentitled Nomenclature of Synthetic Rubbers byHarry L. Fisher and appearing on page 941 of Industrial and EngineeringChemistry, vol. 31, No. 8 (August 1939). By the term elastic we refer tothat property possessed by elastomers of retracting to approximatelytheir original size after having been greatly distorted.)

Such water-dispersed resin may be either a solid or a liquid and maywith advantage be prepared initially as an aqueous dispersion forvemulsifica'tioninto the pigment-binder solution comprising the outerlacquer phase of my composition. Many suitable water-phase resins,particularly the synthetic elastomers, can be prepared by emulsionpolymerization with the production of a so-called polymer emulsion or,in the case of the synthetic elastomers, a latex comprising a dispersionof the resulting polymeric product in the aqueous polymerization bath.(The term dispersion as used herein with reference to the water-phaseresin includes a suspension of a solid resin in an aqueous medium and anemulsion of a liquid resin in an aqueous medium.)

The unusually good resistance to .crocking and the superior color valueexhibited by fabrics decorated inaccorda-nce with myinventionappear tobe due to theuse in the aqueous phase-of those. resins that are bothinsoluble in water (the aqueous phase of the present composition) andinsoluble. in the particular organic solvent or solvents forming thelacquer phase of the present composition. The use of a water-solubleresin in the aqueous phase of the present emulsion in place of such awater-insoluble resin, although increasing the crockfastness of theresulting decorated fabric to some extent in certain cases, tendshowever to induce flocculation of the pigment; and the result is adecreased color value, which can be controlled but only with diflicultyand at considerable expense.

While some improvement in crockfastness can also be obtained-on theother hand, with an emulsion containing an elastomer dissolved in thelacquer phase in place of thepresent waterdispersed resin, the usethereof requires a materially greater amount of such lacquerphasesoluble elastomer to give the same improvement in crockfastness.The color value of the decorated fabric is also impaired especially indeep shades where crock improvement is most needed. In addition, suchlacquer phase-soluble elastomers are generally not resistant todry-cleaning solvents. Moreover, although the elastomers dispersed inthe aqueous phase of the present emulsion can be brought into solutionthrough the use of powerful solvents, such solvents are not only costlybut are generally incompatible with the diluents and resins customarilyemployed in a water-in-lacquer textile-decorating emulsion.

Ithas been my experience, however, that substantially satisfactoryresults with respect to crock-reduction can be obtained even if thewaterphase resin is very slightly soluble in or swellable by thesolvents comprising the lacquer phase pro vided that the dispersedwater-phase resin is so protected by the aqueous phase that'the actualdegree of solubility or swellability is practically negligible; and theuse of such a resin in the aqueous phase of my emulsion is contemplatedas be film-forming, i. e., capable of forming a film upon evaporation ofthe water and the solvents comprising the emulsion. The resulting filmshould preferably be not too hard and horny and is advantageouslyelastic and rubbery in nature, and syn hetic elastomeric substances suchas those specifically mentioned previously are especially adapted forthis purpose.

Examination of the finished fabric indicates that the film formed fromthe water-phase resin appears to reenf-orce the film that is formed bythe pigment binder in the lacquer phase and that binds the pigm nt tothe fabric and, moreover, is unpigmented. In effect, therefore, thewaterphase resin of my improved emulsion may be considered to overpadthe pigment binder without, however, the disadvantageous resultsobtained in the customary two-step overpadding procedure. Whatever theexact explanation may be, it is certain that a decorated fabric havingan exceptional degree of crockfastness can be prepared from the presentpigmented emulsion.

is well known, the customary pigmented water--in-lacquer emulsioncontains an amount of binder in the lacquer phase that is generally acompromise amon three factors: the amount of binder necessary to insurea relatively good degree of crocirfastness, the amount of binder justinsufficient to impart an undesirable degree of boardiness to thefinished fabric, and the cost of the binder; and the resultingcompromise amount is generally insuflicient to provide the necessarydegree of crockfastness except in relatively light shades. With thepresent composition, this compromise amount of pigment binder can bemaintained or even decreased with the production of a substantiallycrockfast, full-color, decorated fabric having an unusually soft handregardless of the depth of shade desired.

The reduction in the degree of croclring accomplished with the instantemulsion can be effected whether a deep or a light shade is desired inthe finished fabric; and my invention thus permits the wide applicationand full utilization of pigments in the decoration of textiles. Fabricscan be colored a deep shade with the present composition, especially onecontaining a film-forming elastomer, with substantial elimination of drycrock and material reduction of wet crock. Particularly importantapplications of my improved emulsion lie in blotch printing, i. e., theprinting of designs containing large areas of solid color, and inpad-dyeing.

An important advantage of my invention is that curing of the Wetdecorated fabric, where a thermcsetting resin. is included in thelacquer phase, can be largely eliminated. All that is necessary, indrying the wet fabric, is to sub- .l'eot it to the conventionaltreatment, for ample, passage over the customary bank. of steam-heateddrying cans or other equipment, to evaporate the water and the solventcontent of the emulsion. These cans are generally maintained at atemperature ranging from 210 to 250 R, which is sufiicient to initiallyset the thermosetting resin but insufficient to completely cure it.Despite the lack of cure of the thermosetting resi the resulting fabricexhibits im proved crock-fastness and possesses a good degree ofwashfastness, which increases on aging as the resin further polymerizesand cures itself. By reason or the elimination of the curing steprequired with previously suggested procedures for the reduction orcroclring and with the use of customary emulsions, the speed at which apigment-decorated fabric is produced can be materially increased; and Ihave been successful in decorating textiles at a rate as high as 200yards per minute in accordance with the present invention. Curing of theinitially set resin can, of course, be practiced but requires theinstallation of special heating and curing equipment.

As is the case with the pigment binder of the lacquer phase, thewater-dispersed resin is deposited on the fabric in discontinuous filmsthat do not bridge over the individual yarns. No appreciable boardiness,accordingly, is imparted to the decorated fabric, which retainssubstantially its initial hand. Moreover, despite the deposition of anadditional discontinuous film of resin on each fiber, the resultingfabric possesses generally a deeper, fuller color value. In com parison.a pigmented emulsion containing an increased amount of resin in thelacquer phase imparts a marked boardiness to the resulting decoratedfabric, the color value or which, especially in the deeper shades, isalso adversely afiected.

The organic solvents forming the lacquer phase of my emulsion must bereadily volatile so that they can be evaporated by passage of the wetfabric over the conventional drying equipment and, of course, must beinsoluble in the water phase of the emulsion. In addition, the organicsolvents must be chosen with respect to their insolubility for thewater-dispersed resin. Typical solvents (without regard to theirinsolubility for all resins suitable for dispersion in the aqueous phaseof the present emulsion) include turpentine, mineral spirits, pine oil,high-aromatic hydrocarbon solvents, e. g., a fraction having a boilingrange of 310 to 375 l t, and the like.

In the preparation of my improved fabricdecorating composition, a colorconcentrate can be first prepared by dissolving the pigment binder inthe organic solvent, dispersing the pigment in the resulting lacquerdesirably in a suitable mill, and then emulsifying an aqueous dispersionof the water-insoluble resin into this lacquer. The pigment may containa suitable dispersing agent and, in the case of organophilic pigments,may be prepared in the form of a thick paste in an appropriate organicsolvent. The aqueous resin dispersion may be prepared by suitablydispersing the resin in water or may be obtained as such in themanufacture of the resin. An emulsifier such as organic solvent-solubleethyl cellulose, aluminum stearate, calcium palmitate, or a dryingoil-modified alkyd resin may be incorporated in the lacquer. Theresulting water-in-lacquer emulsion can then be cut to the desiredprinting or dyeing consistency by adding further organic solvent theretoand then emulsifying additional water thereinto.

Advantageously, however, a vehicle concentrate is simultaneouslyprepared by emulsifying water, which may contain an emulsion stabilizersuch as common salt, into a suitable organic solvent, which may containan emulsifying binder such as an alkyd-type resin dissolved therein.This F concentrated water-in-la-cquer emulsion then be cut withadditional organic solvent, and further water can be emulsifiedthereinto to provide a vehicle or clear having the desired printing ordyeing consistency. The color concentrate can now be cut with thisvehicle in the proportions necessary to produce the specified shade.

Variations of these methods of preparation can, of course, be utilized.For example, the aqueous resin dispersion, instead of being emulsifiedinto the color concentrate, can be added to the vehicle concentrate asitiis being cut with-additional organic solvent. In-such event,thecolorconcen- .trate may consist simplyof a dispersion 'of the pigmentin the solutionof the pigment binder in the organic solvent.

.Moreover, the vehicle concentrate can with advantage be preparedibyemulsifying the aqueous resin dispersion into the organic, solvent,which may have dissolved therein an alkyd-type: resin as an emulsifyingbinder. .A vehicle orclear having the desired printingor dyeingconsistency can then be prepared as indicated above; and the colorconcentrate, whichmay comprise either a pigmentedilacqueror a pigmentedwater-in-lacquer emulsion, can now bexcut with this vehicleintheproportionsnecessary to produce the desired shade. If desired; partof the water-insoluble resin may be contained in the aqueous phase ofthewater-in-lacquer color concentrate.

Care should be observed in the preparation of theseemulsions. thatcoagulation of the particles ofwthewater-dispersed resin on standing issubstantially prevented or eliminated, particularly in the case ofthecolor concentrate as prepared with the water-insoluble resin ,in theaqueous phase. For example, as already indicated, the solvents of thelacquer phase should be insoluble in water; and any water-solublesolvents such as butanol, which may be contained initially in theorganic solvent-soluble resin, should be eliminated as completely aspossible to avoid coagulation of the water-dispersed resin. Again,certain pigments appear to'have a tendency to cause coagulation of thewater-dispersed resin partic ularly if they are not prepared with asufiicient degree of purity;= and stabilizing agents such as the sodiumsalts of alkyl-aryl sulfonates have been found helpful in such casesincounteracting this undesirable effect of such pigments.

Where the present composition is to be utilized in the printing ofa-fabric, it canbeapplied in any convenient manner as from anintagliocylinder. Where it is employed in the dyeing of a fabric, it can beapplied bymeans' of a paddyeing operation; or it can be deposited on thefabric in the form of a thin film by transfer from a roll-coatingmachine. The decorated fabric can be conveniently dried by passage overconventional drying equipment such as a'bank 10f steam-heated dryingcans maintained at a temperature in the range of: 210 to 250 F.; and thedried fabric, if it is desired to do so, can be passed through a curingchamber maintained at a temperature of 300 to 350 F. to cure thethermosetting resin, where it comprises the pigment binder, althoughsuch curing operation is not necessaryto obtain the greatly improvedcrockfastness possible with my emulsion.

The proportions of the several ingredients of the present compositionmay vary -widely and depend largely on the requirements'of the finishedfabric and the nature of the particular application. Generally, inprinting with the present emulsion-the aqueous phase comprises a higherpercentage of the total compositionthan indyeing'therewith-since, as iswell known, the emulsification of an increasing amount of water intosuchan emulsion tends to thicken it. The depth of color desired obviouslygoverns the amount of pigment used. The Water-dispersed resin should besufficient in amount to render the finished fabric satisfactorilycrockfast; and the amount of pigment binder should'simila-rly besufficient-to impart the necessary degree of washfastness I to thefinished fabric.

'Advantageously, the water-dispersed "resin, especiallywhen it comprisesan elastomeryand the pigment are present ina ratio rangingfrom about0.25:1 to :1 by weight. Although some increase in crock-resistance canbe obtained with a lower ratio, satisfactory improvement incrockfastness first becomes appreciably noticeable when the elastomerand the pigment are present in about the indicated minimum ratio. Thereis not much to be gained in utilizing the elastomer and the pigment in aratio greater than the indicated maximum since the shade of theresulting decorated fabric is then so light that crocking no longerpresents a problem.

In this connection, it should be borne in mind that the percentage ofpigment in the present composition and the nature of the emulsion itselfplace a practical limit on the percentage of elastomer that can beincorporated therein in any given instance. Obviously, in a compositioncontaining a relatively high amount of pigment, the practical maximumratio of elastomer to pigment is less than the corresponding maximumratio when the composition contains a relatively low amount of pigment.Since the actual textiledecorating emulsion itself is usually preparedby cutting a color concentrate containing a waterdispersed resin with asuitable vehicle or clear in proportions to produce the desired depth ofshade, obviously the percentage of pigment in the resulting compositiondecreases the more the color concentrate is cut with the clear while theratio of elastomer-to pi ment remains the same. If the vehicle alsocontains an elastomer dispersed in its aqueous phase, then the ratio ofelastomer to pigment obviously increases the more the color concentrateis cut. Moreover, the ratio of the water-dispersed resin to the pigmentis also governed to some extentby the particular pigment selected; forexample, copper phthalocyanine blue requires a larger amount ofelastomer than copper phthalocyanine green for a given degree ofcrockfastness.

Various types of fabrics can be decorated by means of my improvedcomposition and the application of my invention is not limited to thedecoration of any particular fabric. Excellent resistance to crockingand excellent color value without boardiness of the finished fabric areobtained equally well whether the fabric being decorated is composed ofnatural fibers such as cotton, flax, wool, and hair fibers, of syntheticfibers such'as regenerated cellulose, cellulose acetate, polyamide,protein polymer, vinyl polymer, and the like fibers, of inorganic fiberssuch as glass, mineral, or metal fibers, or of mixtures of such fibers.Furthermore, the application of my invention is not limited to the usualtypes of woven or knitted fabrics but may also be used to decorate pilefabrics, paper, orfabrics made by processes such as combing, matting, orfelting, e. g., afabric composed of loosely meshed cotton fibers bondedtogether by the localized application of a resin. The present invention,moreover, is'equally applicable whether a light or a heavy fabric isbeing decorated. ('Iherterm fabric-as used in the claims includes allthese various types of materials as well as yarns, to the decorating Ofwhich my invention is also applicable.)

The following examples are typical illustrations of color concentratessuitable for use in carrying out my invention:

9 EXAMPLE 1 A color concentrate containing a benzidine yellow isprepared by mixing together, in a suitable mixer, the followingingredients (parts by weight in this and other examples) Turpentine 56.650% solution of hydrophobic melamineformaldehyde resin in an equaladmixture of butanol and xylene (e. g., Melmac 245-8) 10.0 Benzidineyellow pigment (tetrazotized dichlorobenzidine coupled withacetoacet-otoluidide) 10.0 Ethyl cellulose (highly ethylated) 0.4

and emulsifying into the resulting pigmented lacquer:

40% aqueous dispersion of an emulsion copolymer of 55% 1,3-butaolieneand 45% acrylonitrile (e. g., Hycar OR-15) 23.0

Th butacliene-acrylonitrile copolymer is insoluble in the turpentineforming the lacquer phase of the resulting Water-in-lacquer emulsion.

EXAMPLE 2 A lacquer containing dispersed copper phthalocyanine green isprepared by suitably mixing the following ingredients:

Mineral spirits 42.2 Pine oil 1.0 Ethyl cellulose (highly ethylated) 0.8Copper phthalocyanine green 6.0

Into this pigmented lacquer is emulsified the following aqueous resindispersion:

12% aqueous dispersion of hydrophobic melamine-formaldehyde resin (e.g., Ciba No. 40) 50.0

Mineral spirits is selected as the solvent for the lacquer phase of theresulting water-in-lacquer emulsion because of its poor solvent powerfor the water-dispersed melamine-formaldehyde resin.

EXAMPLE 3 A blue color concentrate is prepared by mixing the followingingredients:

Turpentine 57.6 Hydrophobic melamine-formaldehyd resin solution ofExample 1 9.0 Pineoil 3.0 Ethyl cellulose (highly ethylated) 0.4 Copperphthalocyanine blue 6.0 v

and emulsifying into the resulting pigmented lacquer:

A color concentrate is prepared by emulsify n into this lacquer:

40% aqueous dispersion of an emulsion copolymer or 67% 1,3-butadiene and33% acrylonitrile (e. g., Hycar OR-25) 25.0

I0 EXAMPLE 5 The following ingredients are mixed to form a pigmentedlacquer:

Turpentine 54.6 Hydrophobic melamine-formaldehyde resin solution ofExample 1 9.0 Ethyl cellulose (highly ethylated) 0.4 Copperphthalocyanine blue 6.0

which lacquer is emulsified with the following aqueous resin dispersionto produce a Water-inlacquer color concentrate:

30% aqueous dispersion of a butyl methacrylate polymer (e. g., MethacrolBP) 30.0

The following example is a typical illustration of a vehicle concentratesuitable for cutting the color concentrates of Examples 1 to 5:

Example I A vehicle concentrate is prepared by forming a lacquer fromthe following:

Mineral spirits 25 drying oil-modified phthalic-glyceride alkyd resin(e. g., Beckasol No. 18) 25 and emulsifying thereinto:

Water 45 Sodium chloride 5 The alkyd resin has a viscosity of V to X onthe Gardner scale and an acid number of 10 to 15.

This vehicle concentrate can then be cut by the addition of furthermineral spirits and water in the proportions necessary to give either aprinting or a dyeing vehicle having the body and the viscosity desired:

Example II A printing vehicle is prepared by adding mineral spirits tothe vehicle concentrate and emulsifying water thereinto in the followingproportions:

Vehicle concentrate of Example I 6 Mineral spirits 20 Water '74 ExampleIII A typical pad-dyeing vehicle is prepared by addition of mineralspirits to the vehicle concentrate and emulsifying water thereinto inthe following proportions:

Vehicle concentrate of Example I 6 Mineral spirits 40 Water 54 Printingpastes and pad-dyeing liquors can be prepared by cutting the colorconcentrates of Examples 1 to 5 with the printing vehicle and thepad-dyeing vehicle of Examples II and III, respectively. The proportionsin which the color concentrate and the respective vehicle are mixeddepend, of course, on the depth of shade desired in the finished fabric.Typical examples of a printing paste and of a pad-dyeing liquor areillustrated by the following:

EXAMPLE A A printing paste giving a deep shade is prepared by cutting acolor concentrate with the printing vehicle in the followingproportions:

Color concentrate of Example 1 1 Printing vehicle of Example II 2 Atextile such as cotton percale printed with this 1'11 paste exhibitssubstantially no cracking, possesses a soft hand, and has a full, evencolor value.

EXAMPLE B l A pad-dyeing liquor giving a medium shade is prepared bycutting a colorconcentrate with the pad-dyeing vehicle in the followingproportions:

Color concentrate of Example 4 1 Pad-dyeing vehicle of Example III Whena textile such as rayon is dyed with this liquor, it is extremelycrockfast, exhibits no particular increase in stiffness, and has a goodcolor.

In both cases the decorated fabric need only be dried in theconventional manner to produce the finished material.

The following example is typical of a vehicle concentrate having thewater-insoluble resin dispersed in its aqueous phase:

Example IV A vehicle concentrate is prepared by emulsifying:

Emulsion copolymer dispersion of Example 4 25.0 Water 7.5

into:

50% solution-in -xylene of a phenolated 41% soya bean oil-modifiedphthahc-glyceride alkyd (e. g., Beckasol P27) 67.5

This vehicle concentrate can then be cut by the addition of furthersolvent and water in the proportions necessary to give a printing or adyeing vehicle or clear having the desired consistency:

Example V Solvent is added to-this vehicle concentrate and Water isemulsified thereinto in the following proportions to produce a printingvehicle:

Vehicle concentrate of Example IV 5 Mineral spirits Water '75 A typicalcolor concentratethat can be cut by The water is separated, and apigment binder and additional solvent are admixed with the pigmentdispersion to reduce the pigment concentration to 20%:

Pigment dispersion. (water-free) 4-5 Solvent naphtha (as above) 35Hydrophobic melamine-formaldehyde resin.

solution of Example 1 20 The resulting lacquer is emulsified with anelastomer latex to produce a color-concentratecontaining 15% pigment:

Pigmented lacquer 75 Emulsion copolymer dispersion of Example 4 Aprinting pastercan be prepared by cutting the I 12 color concentrate ofExample. 6 with the vehicle or clear of Example V:

EXAMPLE C A printing paste giving a medium shade is prepared by cuttingsuch color concentrate with such printing-vehicle in the followingproportions:

Color concentrate-ofExample 6 l Printingavehicle of Example V 10 Atextile such as cotton printed with this pastels remarkably free fromwet crocking, has a soft hand and presents an evenly colored appearance.

I claim:

1. A textile decorating composition comprising a-continuousorganiciphase containing a volatile organic material consistingessentially of waterimmiscible liquid, said organic. phase having,dispersed therein a water-insoluble pigment color, water, and awater-insoluble, linean-rubber-like diolefin polymer which is dispersedin said water and is-substantially insoluble in said organic liquid andis-adapted to reduce removal of said pigment, through rubbing, fromcloth decorated with the composition.

A textile decorating composition comprising a. continuous organic phaseconsisting essentially of a volatile water-immiscible organic solventsolution of a thermosetting. resin, having dis persed therein awater-insoluble pigment color, water, and a water-insoluble, linear,rubber-like diolefin polymer which is dispersed in said water and issubstantially insoluble in the organic solvent and is adapted to reduceremoval of said pigment, through rubbing, from cloth decorated with thecomposition.-

3. A textile, decorating composition comprising a continuous organicphase containing. a volatile organic material consisting essentially ofwaterimmiscible liquid and a dispersed Water-insoluble pigment color,and, a-dispersed aqueous .phase containing, a water-insoluble, linear,rubber-like diolefin, polymer which is substantially insoluble insaidprganicdiquid, and is adapted to reduce removal of said pigment,through rubbing, from cloth decorated with the composition.

4. A textile decorating composition comprising a continuous organicphase-consisting. essentially of a volatile Water-immiscible organicsolvent solution. of anthermosetting resin and a dispersedwater-insoluble. pigment color; anda dispersed aqueous phase containinga water-insoluble, linear, rubber-likediolefin-polymer which issubstantiallyinsoluble-in said organic solvent and is adapted to reduceremoval of said pigment, through rubbing, from cloth, decorated with.the composition.

5. A textile decorating composition comprising a continuous organicphase-consisting essentially of a volatile water-immiscible organicsolvent solution. ofna thermosetting-resin and dispersed wateninsolublepigmentcolor, and a dispersed aqueous phase containing aWater-insoluble, linear,- rubber-like butadiene-acrylonitrile copolymer.which is substantially insoluble in said organic solvent and is adaptedto reduce removal of said pigment, through rubbing, from clothdecorated. with the composition.

6. A textile decorating composition comprising a continuous organicphaseconsisting essentially of a volatile, water-immiscible organic solventsolution of a thermosetting resin and a dispersed water-insolublepigment. color, and a dispersed 0 aqueous phase containing awater-insoluble, linear,rubber-1ike butadiene-acrylonitrile copolymerReferences Cited in the file of this patent which is substantiallyinsoluble in said organic UNITED STATES PATENTS solvent and is adaptedto reduce the removal of said pigment, through rubbing, from cloth deco-Number Name Date rated with the composition, and wherein the 5 2383'937Klenle et Sept 1945 ratio of said copolymer to pigment is 0.25:1 toFOREIGN PATENTS 100:1 by wegiht.

7. A textile decorating fabric having thereon Numbg; Country t the driedproduct of claim 1. 349,903 Great Britain May 27, 1931 8. A textilefabric having thereon the dried 19 349,933 Great Britain Ma,y 27 1931product of claim 5.

1. A TEXTILE DECORATING COMPOSITION COMPRISING A CONTINUOUS ORGANICPHASE CONTAINING A VOLATILE ORGANIC MATERIAL CONSISTING ESSENTIALLY OFWATERIMMISCIBLE LIQUID; SAID ORGANIC PHASE HAVING DISPERSED THEREIN AWATER-INSOLUBLE PIGMENT COLOR, WATER, AND A WATER-INSOLUBLE, LINEAR,RUBBER-LIKE DIOLEFIN POLYMER WHICH IS DISPERSED IN SAID WATER AND ISSUBSTANTIALLY INSOLUBLE IN SAID ROGANIC LIQUID AND IS ADAPTED TO REDUCEREMOVAL OF SAID PIGMENT, THROUGH RUBBING, FROM CLOTH DECORATED WITH THECOMPOSITION.